1-carbalkoxy-2-cyano-vinyl-(thiono)-phosphoric ((phosphonic) acid esters of ester amides

ABSTRACT

1-CARBALKOXY-2-CYANO-VINYL-(THIONO)-PHOSPHORIC (PHOSPHONIC) ACID ESTERS OR ESTER AMIDES OF THE FORMULA   IN WHICH R and R&#39;&#39;&#39;&#39; are alkyl of 1 to 6 carbon atoms, R&#39;&#39; is alkyl, alkoxy or monoalkylamino of 1 to 6 carbon atoms, or phenyl, R&#39;&#39;&#39;&#39;&#39;&#39; is hydrogen or alkyl of 1 to 20 carbon atoms, and X is oxygen or sulfur, WHICH POSSESS INSECTICIDAL AND ACARICIDAL PROPERTIES.

United States Patent [1 1 Maurer et al.

[22] Filed: Mar. 14, 1973 [21] Appl. No.1 341,188

[30] Foreign Application Priority Data Mar. 17, l972 Germany 22l2906 [52] US. Cl 260/940, 260/465.4, 260/973,

[51] Int. Cl ..A01n 9/36, C07f 9/08, C07f 9/16 [58] Field of Search 260/940 [56] References Cited UNITED STATES PATENTS 3,784,589 1/1974 Large 260/940 x FOREIGN PATENTS OR APPLICATIONS 654,748 10/1964 Belgium 260/940 [451 Jan. 21, 1975 Primary Examiner-Lorraine A. Weinbcrgcr Assistant Examiner-Richard L. Raymond Attorney, Agent, or Firm-Burgess, Dinklage & Sprung [57] ABSTRACT l-carbalkoxy-2-cyan0-vinyl (thiono)-phosphoric (phosphonic) acid esters or ester amides of the formula in which R and R" are alkyl of l to 6 carbon atoms,

R is alkyl, alkoxy or monoalkylamino of l to 6 carbon atoms, or phenyl,

R' is hydrogen or alkyl of l to 20 carbon atoms,

and X is oxygen or sulfur,

which possess insecticidal and acaricidal properties.

7 Claims, No Drawings 1-CARBALKOXY-2-CYANO-VINYL-(THIONO)- PHOSPHORIC ((PHOSPHONIC) ACID ESTERS OF ESTER AMIDES Soc., Japan 25, 61 65 (1961), Japanese Patent Specifications 2926 (1960) and 12217 (1966), and Belgian Patent Specification 654,748, that cyanoand/or carbalkoxy-substituted vinyl-(thiono)-phosphoric(- phosphonic) acid esters, such as 0,0-diethyl-O-(1- methyl-2cyano-2-phenylvinyl)-thiono-phosphoric, O- ethyl-O-( 1-methyl-2-cyano-2-carbethoxyvinyl)- ethaneand O-ethyl-O-(1-carbethoxy-2-cyano-2- phenylvinyl)-phenyl-phosphonic acid ester, possess insecticidal properties.

The present invention provides l carbalkoxy-2- cyanovinyl-(thiono)-phosphoric(phosphonic) acid esters or ester amides of the general formula in which R and R are alkyl of l to 6 carbon atoms, R is alkyl, alkoxy or monoalkylamino of 1 to 6 carbon atoms, or phenyl, R' is hydrogen or alkyl of 1 to carbon atoms, and X is oxygen or sulfur. Preferably R and R" are lower alkyl of l to 4 carbon atoms, R is lower alkyl, alkoxy or monoalkylamino of l to 4 carbon atoms or phenyl, and R is hydrogen or alkyl with l to 16 carbon atoms.

The alkyl, alkoxy or monoalkylamino radicals may of course be straight-chain or branched radicals.

The general formula (I) embraces the cisand transisomers of the constitutions (II) and (III) below, as well as mixtures of these isomers.

X X R R O E.P"O\ /CN R" R. IC=

R"O C R"O O CN (11) (III) Surprisingly, the l-earbalkoxy-2-cyanovinyl- (thionol)-phosphoric(phosphonic) acid esters or ester amides according to the invention show a considerably higher insecticidal, in particular soil-insecticidal, and acaricidal activity than previously known compounds of analogous constitution and of the same direction of activity. The compounds moreover also act very well against hygiene pests and pests of stored products. The

substances according to the invention therefore represent a genuine enrichment of the art.

Furthermore, the compounds contribute to the reduction of the continuing requirement of new active compounds in the field of pesticides. This requirement originates in that, largely for reasons of environment protection, ever higher demands are being made of the commercially available agents, such as low toxicity to warm-blooded animals and low phytotoxicity, rapid degradation in and on the plant in short minimum intervals to be observed between spraying with pesticide and harvesting, effectiveness against resistant pests, etc.

The invention also provides a process for the production of a 1-carbalkoxy-2-cyanovinyl-(thiono)-phosphoric(phosphonic) acid ester or ester amide of the formula (1) in which an alkylnitrile of the general formula is reacted with an oxalic acid diester of the general formula II II in alkaline medium, and the resulting compound of the general formula is reacted with a (thiono)-phosphoric(phosphonic) acid ester halide or ester amide halide of the general formula no if P-Hal (VII) 0 o HaOC H I! ll 18.) on on c u o-c-c-oc H 5 2 5 2 5 -2xC I-I OH (Va) co c n NC(H)C=C\ 0H0 (VIa) co H s 2 2 1b) NC a c c (C H O) P-Cl ONa (VIa) (VIIa) -NaCl E 3 2 2 (C2H50)2P-0-C=C(H)CH The (thiono)-phosphoric(phosphonic) acid ester halides or ester amide halides (VII) and the alkyl nitriles (IV) and the oxalic acid diesters (V) required as starting materials are known from the literature and can readily be produced even on an industrial scale.

As examples of alkyl nitriles to be reacted according to the process, there are mentioned in particular: the nitriles of acetic, propionic, n-butyric, and iso-butyric acid, n-valeric acid, caproic acid, caprylic acid, capric acid, laurie acid and palmitic acid.

Of oxalic acid diesters to be used according to the process, particularly suitable are:

di-methyl or di-ethyl, di-n-propyl, di-iso-propyl, di-nbutyl, di-iso-butyl and di-sec.-butyl oxalates.

As (thiono)-phosphoric(phosphonic) acid ester halides or ester amide halides, there are mentioned in particular: 0,0-dimethyl-, 0,0-diethyl-, 0,0-dipropyl-, 0,0-di-isopropyl-, 0,0-di-n-butyl-, 0,0-di-sec.-butyl-, 0,0-di-tert.-butyl-, 0,0-di-isobutyl-, O-methyl-O- ethyl-, O-ethyl-O-isopropyl-, O-ethyl-O-n-butyland O-n-propyl-O-n-butyl-phosphoric acid ester chloride and their thiono analogues; further, O-methyl-, O- ethyl-, O-n-propyl-, O-iso-propyl-, O-n-butyl-, O-isobutyl-, O-tert.-butyland O-sec.-butyl-methane-, -ethane-, -n-propane-, -iso-propane-, -n-butane-, -isobutane-, -tert.-butane-, -see.-butaneor -phenylphosphonic acid ester chloride and the corresponding thiono analogues as well as O-methyl-, O-ethyl-, O-npropyl-, O-iso-propyl-, O-n-butyl-, O-iso-butyl-, O-sec.- butyland O-tert.-butyl-N-methylor -N-ethyl-, -N-npropy l-, -N-iso-propyl-, -N-n-butyl-, -N-iso-butyl-, -N- see.-butyland -N-tert.-butyl-phosphoric acid ester amide chloride and their thiono analogues.

The process according to the invention is preferably carried out in the presence of a solvent or diluent. As such, practically all inert organic solvents are suitable. These include, above all, aliphatic and aromatic optionally chlorinated hydrocarbons. The first step of the process is preferably caused to proceed in benzene, toluene, xylene, an ether such as diethyl ether or dibutyl ether, or an alcohol such as ethanol, iso-propanol or tert.-butanol, while the second step is carried out particularly advantageously in benzene, toluene, xylene, benzine, methylene chloride, chloroform, carbon tetrachloride, chlorobenzene, an ether such as diethyl ether or dibutyl ether or dioxane, a ketone such as acetone, methyl ethyl ketone, methyl isopropyl ketone or methyl isobutyl ketone, a nitrile such as acetonitrile or propionitrile, or an amide such as dimethyl formamide.

As an alkaline agent to ensure that the first step is carried out in alkaline medium, one may use an alkali metal alcoholate, especially sodium methylate, sodium ethylate, sodium isopropylate or potassium tert.- butylate.

The reaction temperatures can be varied within a fairly wide range. In general, the reactions are carried out at about 20 to 120C, preferably about 75 to C in the first step and about 30 to 50C in the sec ond step.

The reactions are, in general, carried out at normal pressure.

When carrying out the process, the starting materials are, in general, used in equimolar proportion. Expediently, a mixture of the nitrile component, the oxalic acid diester and the alkali is heated, without, or in a suitable, solvent, to the elevated temperatures stated for several hours. After cooling of the mixture, the salt formed is either directly filtered off with suction or the reaction mixture is first poured into ether and the precipitate is then filtered off with suction and dried.

The salt-like intermediate products formed are suspended in a suitable solvent, and the phosphoric acid ester component is added. After several hours reaction of the said elevated temperatures, the mixture is poured into a solvent, for example benzene, the organic phase is washed, dried and worked up in customary manner.

The substances according to the invention are obtained in most cases in the form of colored oils, some of which cannot be distilled without decomposition but, by so-called slight distillation", that is, longer heating to moderately elevated temperatures undcr reduced pressure, can be freed from the last volatile components and in this way can be purified. Refractive indices are particularly useful for their characterization. If the products are obtained in crystalline form, they can be characterized by their melting points.

As already mentioned, the new l-carbalkoxy-Z- cyanovinyl-(thiono)-phosphoric(phosphonic) acid es ters or ester amides are distinguished by an outstanding insecticidal (especially soil-insecticidal) and acaricidal effectiveness against crop pests, hygiene pests and pests of stored products. They possess a good activity both against sucking and biting insects, and mites (Acarina At the same time they exhibit a low phytotoxicity.

For these reasons the compounds according to the invention can be used with success as pesticides in crop protection and the protection of stored products, as well as in the hygiene field.

To the sucking insects there belong, in the main, aphids (Aphidae) such as the green peach aphid (Myzus persicae), the bean aphid (Doralis fabaer), the bird cherry aphid (Rhopalosiphum padi), the pea aphid (Macrosiphum pisi) and the potato aphid (Macrosiphum solanifolii), the currant gall aphid (Cryprumyzus korschelti), the rosy apple aphid (Sappahis mali), the mealy plum aphid (Hyalopterus arundinis) and the cherry black-fly (Myzus cerasi); in addition, scales and mealybugs (Coccina), for example the oleander scale (Aspidiotus hederae) and the soft scale (Lecanium hesperidum) as well as the grape mealybug (Iseudmuccus marilimus); thrips (Thysanoptera), such as Hercinothrips femoralis, and bugs, for example the beet bug (Piesma quadrata), the red cotton bug (Dysdercus intermedius), the bed bug (Cimex lecmlarius), the assassin bug (Rhodnius prolixus) and Chagas bug (Trialoma infestans) and, further, cicadas, such as Euscelis bilubalus and Nephotettix bipunctatus.

In the case of the biting insects, above all there should be mentioned butterfly caterpillars (Lepidoptera) such as the diamond-back moth (Plulellu maculipennis), the gypsy moth (Lymamria dispar), the browntail moth (Euproctis chrysorrhoea) and tent caterpillar (Malacosoma neustria); further, the cabbage moth (Mamestra brassicae) and the cutworm (Agrotis segeturn), the large white butterfly (Pieris brassicae), the small winter moth (Cheimatobia brumata), the green oak tortrix moth (Tortrix viridana), the fall armyworm (Laphygma frugiperda) and cottom worm (Prodenia litura), the ermine moth (Hyponomeuta padella), the Mediterranean flour moth (Ephestia kiihniella) and greater wax moth (Galleria mellonella).

Also to be classed with the biting insects are beetles (Coleoptera), for example the granary weevil (Sirophilus granarius Calandra granaria), the Colorado beetle (Leptinotarsa decemlineata), the dock beetle (Gastrophysa viridula), the mustard beetle (Phaedon cochleariae), the blossom beetle (Meligethes aenus), the raspberry beetle (Byturus tomentosus), the bean weevil (Bruchidius Acanthoscelides obtectus), the leather beetle (Dermestes frischi), the khapra beetle (Trogoderma granarium), the flour beetle (Tribolium castaneum), the northern corn billbug (Calaridra or Sitophilus zeamais), the drugstore beetle (Stegobium paniceum), the yellow mealworm (Tenebrio molitor) and the saw-toothed grain beetle (Oryzaephilus Surinamensis), and also species living in the soil, for example wireworms (Agriotes spec.) and larvae of the cockchafter (Melolontha melolontha); cockroaches, such as the German cockroach (Blattella germanica), American cockroach (Periplaneta americana), Madeira cockroach (Leucophaea or Rhyparobia maderae), oriental cockroach (Blatta orientalis), the giant cockroach (Blaberus giganteus) and the black giant cockroach (Blaberus fuscus) as well as Henschoutedenia flexivitta; further, Orthoptera, for example the house cricket (Gryllus domesticus); termites such as the eastern subterranean termite (Reticulitermes flavipes) and Hymenoptera such as ants, for example the garden ant (Lasius niger).

The Diptera comprise essentially the flies, such as the vinegar fly (Drosophila melanogaster), the Mediterranean fruit fly (Ceratitis capitata), the house fly (Musca domestica), the little house fly (Fannia canicularis), the black blow fly (Phormia regina) and bluebottle fly (Calliphora erythrocephala) as well as the stable fly (Stomoxys calcitrans); further, gnats, for example mosquitoes such as the yellow fever mosquito (Aedes aegypti), the northern house mosquito (Culex pipiens) and the malaria mosquito (Anopheles stephensi).

With the mites (Acari) there are classed, in particular, the spider mites (Tetranychidae) such as the twospotted spider mite (Tetranychus urticae) and the European red mite (Paratetranychus pilosus Panonychus ulmi), gall mites, for example the black currant gall mite (Eriophyes ribis) and tarsonemids, for example the broad mite (Hemitarsonemus latus) and the cyclamen mite (Tarsonemus pallidus); finally, ticks, such as the relapsing fever tick (Ornizhodorus moubata).

When applied against hygiene pests and pests of stored products, particularly flies and mosquitoes, the process products are also distinguished by an outstanding residual activity on wood and clay, as well as a good stability to alkali on limed substrates.

The active compounds according to the instant invention can be utilized, if desired, in the form of the usual formulations or compositions with conventional inert (i.e. plant compatible or herbicidally inert) pesticide diluents or extenders, i.e. diluents, carriers or extenders of the type usable in conventional pesticide formulations or compositions, e.g. conventional pesticide dispersible carrier vehicles such as gases, solutions, emulsions, suspensions, emulsifiable concentrates, spray powders, pastes, soluble powders, dusting agents, granules, etc. These are prepared in known manner, for instance by extending the active compounds with conventional pesticide dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g. conventional pesticide surface-active agents, including emulsifying agents and/or dispersing agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents. The following may be chiefly considered for use as conventional carrier vehicles for this purpose: aerosol propellants which are gaseous at normal temperatures and pressures, such as freon; inert dispersible liquid diluent carriers, including inert organic solvents, such as aromatic hydrocarbons (e.g. benzene, toluene, xylene, alkyl naphthalcnes, etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g. chlorobenzenes, etc.), cycloalkanes (e.g. cyclohexane, etc), paraffins (e.g. petroleum or mineral oil fractions), chlorinated aliphatic hydrocarbons (e.g. methylene chloride, chloroethylenes, etc.), alcohols (e.g. methanol, ethanol, propanol, butanol, glycol, etc.) as well as ethers and esters thereof (e.g. glycol monomethyl ether, etc.), amines (e.g. ethanolamine, etc.), amides (e.g. dimethyl formamide, etc), sulfoxides'(e.g. dimethyl sulfoxide, etc.), acetonitrilc, ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), and/or water;.as well as inert dispersible finely divided solid carriers, such as ground natural minerals (e.g. kaolins, clays, alumina, silica, chalk, i.e. calcium carbonate, talc, attapulgite, montmorillonite, kieselguhr, etc.) and ground synthetic minerals (e.g. highly dispersed silicic acid, silicates, e.g. alkali silicates, etc.); whereas the following may be chiefly considered for use as conventional carrier vehicle assistants, e.g. surface-active agents, for this purpose: emulsifying agents, such as non-ionic and- /or anionic emulsifying agents (e.g. polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfates, alkyl sulfonates, aryl sulfonates, albumin hydrolyzates, etc., and especially alkyl arylpolyglycol ethers, magnesium stearate, sodium oleate, etc.); and/or dispersing agents, such as lignin, sulflte waste liquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtures with one another and/or with such solid and/or liquid dispersible carrier vehicles and/or with other known compatible active agents, especially plant protection agents, such as other insecticides and aearicides, or rodenticides, fungicides, bactericides, nematocides, herbicides, fertilizers, growth-regulating agents, etc., if desired, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granules which are thus ready for use.

As concerns commercially marketed preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about 01-95% by weight, and preferably 05-90% by weight, of the mixture, whereas carrier composition mixtures suitable for direct application or field application generally contemplate those in which the active compound is present in an amount substantially between about 00001 and 10%, preferably 0.01 and 1%, by weight of the mixture.

Thus, the present invention contemplates over-all compositions which comprises mixtures of a conventional dispersible carrier vehicle such as (l) a dispersible inert finely divided carrier solid, and/or (2) a dispersible carrier liquid such as an inert organic solvent and- /or water preferably including a surface-active effective amount of a carrier vehicle assistant, e.g. a surfaceactive agent, such as an emulsifying agent and/or a dispersing agent, and an amount of the active compound which is effective for the purpose in question and which is generally between about 0.0001 and 95%, and preferably 0.01 and 95%, by weight of the mixture.

The active compounds can also be used in accordance with the well known ultra-low-volume process with good success, i.e. by applying such compound if normally a liquid, or by applying a liquid composition containing the same, via very effective atomizing equipment, in finely divided form, e.g. average particle diameter of from 50 to 100 microns, or even less, i.e. mist form, for example by airplane crop spraying techniques. Only up to at most about a few liters/hectare are needed, and often amounts only up to about to 1000 g/hectare, preferably 40 to 600 g/hectare, are sufficient. In this process it is possible to use highly concentrated liquid compositions with said liquid carrier vehicles containing from about to about 95% by weight of the active compound or even the 100% active substance alone, e.g. about 20 to 100% by weight of the active compound.

Furthermore, the present invention contemplates methods of selectively killing, combating or controlling pests, e.g. insects and acarids, which comprises applying to at least one of correspondingly (a) such insects, (b) such acarids, and (c) the corresponding habitat thereof, i.e. the locus to be protected, a correspondingly combative or toxic amount, i.e. an insecticidally or acaricidally effective amount, of the particular active compound of the invention alone or together with a carrier vehicle as noted above. The instant formulations or compositions are applied in the usual manner, for instance by spraying, atomizing, vaporizing, scattering, dusting, watering, squirting, sprinkling, pouring, fumigating, dressing, encrustation, and the like.

It will be realized, of course, that the concentration of the particular active compound utilized in admixture with the carrier vehicle will depend upon the intended application. Therefore, in special cases it is possible to go above or below the aforementioned concentration ranges.

The synthesis, unexpected superiority and outstanding activity of the particular new compounds of the present invention are illustrated, without limitation, by the following examples.

EXAMPLE 1 a. A mixture of 108 g (2 moles) sodium methylate, 82 g (2 moles) acetonitrile and 236 g (2 moles) oxalic acid dimethyl ester was heated to 80 to 90C for 4 hours. After cooling, the reaction mixture was poured into 1 liter of ether. The precipitate was filtered off with suction and dried in a desiccator. I g (57% of theory) of the sodium salt of 3-cyanopyruvic acid methyl ester were obtained.

b. 29.8 g (0.2 mole) of the sodium salt obtained under (a) were suspended in 200 ml aeetonitrile. To this suspension were added dropwise 34.4 g (0.2 mole) O-ethylethanethionophosphonic acid ester chloride and the mixture was allowed to after-react fora further 4 hours at 40C. The reaction mixture was then poured into 300 ml benzene, the benzene solution was subsequently washed with saturated sodium bicarbonate so lution and water. and dried over sodium sulfate. the solvent was drawn off, and the residue was distilled. 35 g (66.5% of theory) of the compound of the above constitution were obtained in the form of a yellow oil with the refractive index n 1.4969 and the boiling point l35C/0.0l mm Hg.

EXAMPLE 2 Analogously to Example 1(a), from 1 18 g (1 mole) oxalic acid dimethyl ester, 55 g l mole) propionitrile and 113 g (1 mole) potassium tert.-butylate in l mole methanol there were obtained g (78% of theory) of the potassium salt of 3-methyl-3-cyanopyruvic acid methyl ester.

To 35.8 g (0.2 mole) of this salt were added dropwise 32 g (0.2 mole) 0,0-dimethylthionophosphoric acid ester chloride. After 4 hours heating to 40C the reaction mixture was cooled and poured into 300 ml benzene, the mixture was washed with saturated sodium bicarbonate solution and water and, after drying over sodium sulfate had been effected, the solvent was drawn off. 26 g (50.5% of theory) of a red oil with the refractive index n 1.4948 were obtained.

EXAMPLE 3 (30 0 11 I N CH -(CH ]C=C 4 Analogously to Example 1(a), from oxalic acid diethyl ester, n-stearyl acid nitrile and potassium tert.- butylate in tert.-butanol there was obtained the potassium salt of 3-stearyl-3-cyanopyruvic acid ethyl ester.

To a suspension of 38.7 g of this salt in 350 ml dimethyl formamide were added dropwise, at 40C, 18.8 g 0,0-diethylthionophosphoric acid ester chloride and the mixture was heated to 60C for a further 4 hours. The precipitate was then filtered off, the dimethyl formamide was drawn off under reduced pressure, the residue was poured into water, the aqueous solution was extracted with methylene chloride, the organic phase was washed and dried, and the solvent was drawn off. After slight distillation of the residue there were obtained 28 g (56.6% of theory) of an oil with the refractive index n,, I 1.4748.

EXAMPLE4 0 11 NC 1i )C=C 0-(OCH 5 Analogously to Example 1(a), from potassium tert.- butylate, oxalic acid diethyl ester and i-valeric acid nitrile in ethanol there was obtained the potassium salt of 3-i-propyl-3-cyanopyruvic acid ethyl ester.

To 44.2 g (02 mole) of this salt were added dropwise 32 g (0.2 mole) 0,0-dimethylthionophosphoric acid ester chloride. After 4 hours heating to 40C, the mixture was cooled and poured into 300 ml benzene, the benzene solution was washed with saturated sodium bicarbonate solution and water; after drying over sodium sulfate had been effected the solvent was drawn off and 29.3 g (48% of theory) of a yellow oil with the refractive index n 1.4830 were obtained.

EXAMPLE 5 A mixture of 339 g (3 moles) potassium tort.-

butylate, 600 ml ethanol, 438 g (3 moles) oxalic acid diethyl ester and 291 g (3 moles) capronitrile was heated under reflux for 4 hours, 3 liters of ether were added to the cooled solution, the salt formed was filtered off with suction and dried.

To 47.0 g (0.2 mole) of this salt in 200 ml acetonitrile were added dropwise 32 g 0,0-dimethylthionophosphoric acid ester chloride, and the mixture was allowed to after-react for 4 hours at C. The reaction mixture was then poured into 300 ml benzene, washed with saturated sodium bicarbonate solution and water and dried over sodium sulfate. After the solvent had been drawn off there remained behind a colorless oil. The yield was.70% of theory, the refraction index was n,, 1.4815.

EXAMPLE 6 In analogous manner other compounds were synthesized, including prior art compounds outside the scope of the present invention. The full structures of many compounds synthesized are set forth in Table 1 while 5 in Table 2 in different sequence there are set forth the radicals of the compounds of Table 1 plus Examples 1 to 5 plus others along with their yields and physical properties.

Table 1 Compound No. Formula N (c a )0 1 c v (known) 6 5 2 5 2 N s c0 0 (known) NC(O6H5)C=Q\ I O oc a o cs5 2 nc(ca )c= (3) 3 3)2 co c a (4) NC(CH )c=C: 2 2 5 s an r 2 2 (5) no(ca )c=c: c a o a s 3 co 0 a 2 2 5 (6) NC(nC H )C=d:

s ,CO2C2H5 NC(I1C H )C: (7) 3 7 E:c a S 0011 co 0 a 2 2 5 (8) Nc(ic n. )c c Compound No.

Table 1 (continued) Formula g OCH 3,862,269 13 1 Table 1 (continued) Compound No Formula 2 (24) lie-CH: o N207}! Compound No.

Table 1 (continued) Formula NC-CH= NC-CHI= Table 2 (continued) ompound x 1 efractive index Yield R No R Rn R111 C/mm Hg) Bolling point 2o 69 S s 'l s v 2 5 5 7 Slightlydistilled 3 59 49 5 slightly distilled 1 77 3 50 S slightly distilled n 65 3 51 3 2 slightly distilled D 4897 72 70 v 3 s 2 5 3 7 2 5 slightly distilled D EXAMPLE 7 Table 3-Continued Drosophila [6M (Drosophilu test) i" w m Solvent: 3 parts by weight acetone Act1ve compound Cfoncte ntration ljDegrce 01 0 ll I Emulsifierz 1 part by weight alkylarylpolyglycol ether pou1d if1 "/s b y z iif' t 'g To produce a suitable preparation of active com- Weighl l y pound, 1 part by weight of the active compound was 0 l mixed with the stated amount of solvent containing the 0:01 100 stated amount of emulsifier, and the concentrate was 83 diluted with water to the desired concentration. (12) 1 ml of the preparation of the active compound was 0.001 100 applied with a pipette to a filter paper disc of 7 cm diameter. The wet disc was placed in a glass vessel con- 0.1 100 taining 50 vinegar flies (Drosophila melanogaster) and (13) 8-8: covered with a glass plate. 010001 100 After the specified periods of time, the destruction (H 100 was determined as a percentage: 100% means that all (M) the flies were killed; 0% means that none of the flies 0.0001 100 were killed. 15) 0.01 100 The active compounds, their concentrations, the (mm evaluation times and the degree of destruction can be g- 100 .1 100 seen from the following Table 3. (mm 00 0.0001 100 Table 3 0.00001 0.1 100 40 (17) 0.01 100 (Drosophila test) '20 Active compound Concentration Degree of 0 of active comdestruction pound in '70 by in after (18) 8'82 weight 1 y '1 100 19) 0.01 100 (1) 0.1 20 (known) 0.01 0 818801 (2) 0.1 100 65 8-? g 20) 0.01 100 0.001 100 091 100 0.1 100 0001 (21) 0.01 100 0.1 100 0.001 100 0.01 100 0.0001 100 0.001 :88 0.1 100 00001 (22) 0.01 100 0.1 100 0001 100 (5) 0.01 100 0.1 100 0.001 100 23 0.01 100 0.0001 100 0.001 100 0.1 100 0.1 100 (6) 0.01 100 (24 0.01 100 0.001 100 0.001 100 0.0001 100 0.1 100 01 100 (25) 0.01 100 (7) 0.01 100 0001 100 0.001 100 00001 100 0.0001 [00 0.00001 40 0.1 100 0.01- 100 (s) 0.01 100 (26) 0.01 100 0.001 100 0.001 100 0,1 100 0.0001 100 0.01 100 0.1 100 9) 0.001 100 (27) 001 0.0001 100 0001 100 '01 100 0.0001 X0 001 100 0.1 100 10 100 (28) 0.01 100 Table 3-Continued Table 4-Continued (Drosophila test) (Plutella test) Act1ve compound Concentration Degree of Active compound Concentration Degree of of active comdestruction 5 of active comdestruction pound in by in after pound in '70 by In '71 after weight 1 day weight 3 days 0.001 100 0.001 110 0.0001 100 0.1 100 0.00001 100 21 0.01 100 -1 1 0.1 100 (29) 0,01 100 34) 0.01 100 0.001 90 0.1 100 0.1 100 22 0.01 100 (30) 0.01 100 0 100 0.001 100 (23) 0.01 100 0.0001 40 0.1 100 0.1 100 25) 0.01 100 (31) 0.01 100 0.1 100 0.001 100 27) 0.01 100 0,1 100 0.1 100 (32) 0.01 100 28) 0.01 100 0.001 100 0.1 100 (35) 0.01 100 20 0.001 100 EXAMPLE 8 (H (29) 0.01 100 Plutella test 01 30) 0.01 100 Solvent: 3 parts by we1ght acetone (H 100 Emulsifier: 1 part by weight alkylarylpolyglycol ether (36) To produce a suitable preparation of active com- 5 (48) 8:2 pound, 1 part by weight of the active compound was 0.001 75 mixed with the stated amount of solvent containing the (49) 8'2 stated amount of emulsifier and the concentrate was diluted with water to the desired concentration.

Cabbage leaves (Brassica oleracea) were sprayed 30 with the preparation of the active compound until dew EXAMPLE 9 moist and were then infested with caterpillars of the Tetranychus test (resistant) diamond-back moth (Plulella maculipennis). Solvent; 3 parts by weight acetone After the spec1fied perlods of t1me, the degree of de- Emulsifier: 1 part by weight alkylarylpolyglycol ether struction was determined as a percentage 100% means To produce a suitable preparation of active comthat all the caterpillars were killed whereas 0% means pound, 1 part by weight of the active compound was that none of the caterpillars were killed. mixed with the stated amount of solvent containing the The active compounds, the concentrations of the acstated amount of emulsifier and the concentrate so obtive compounds, the evaluation times and the results tained was diluted with water to the desired concentracan be seen from the following Table 4. 40 tion,

Table 4 Bean plants (Phaseolus vulgaris), which had a height of a roximatel 10-30 cm., were s ra ed with the PP y P (Plumb test) preparation of act1ve compound untll dr1pp1ng wet. Active compound Concentration Degree of These bean plants were heavily infested with the two f E- lg f i g spotted spider mite (Tetranychus urticae) in all stages OH I I fimighl y 3 days of development.

After the specified periods of time, the effectiveness La 8-2 8 of the preparation of active compound was determined (2) 100 by counting the dead mites. The degree of destruction 8-? 8 thus obtained was expressed as a percentage: 100% (4) 00 means that all the spider mites were killed whereas 0% 0.1 100 means that none of the spider mites were killed. (7) 8'? :88 The active compounds, the concentrations of the ac- (3) 5 5 tive compounds, the evaluation times and the results 0.1 100 1 (9) 0.01 100 can be seen from the following Tab e 5 0.1 100 (11) 0.01 100 Table 5 (H 00 (Tetranychus test resistant) (l3) 0.0l 100 Active Concentration of Degree of 0.l I00 compound active compound destruction in (14) 001 [00 in "/1 by weight after 2 days (H lOO (known) (16) 0.01 100 (2) (1.1 0

0.1 100 (known) (18) 0.01 100 (16) 0.1 )0 0.1 100 (17) 0.1 (19) 0.01 (19) ()1 100 0.1 100 (37) 9s (33) 0.01 100 (21) 90 Table Continued (Tetranychus test/ resistant) LT test for Diptera Test insects: Musca domestica Solvent: acetone 2 parts by weight of active compound were dissolved in 1000 parts by volume of solvent. The solution so obtained was diluted with further solvent to the desired lower concentrations.

2.5 ml of the solution of active compound were pipetted into a Petri dish. On the bottom of the Petri dish there was a filter paper with a diameter of about 9.5 cm. The Petri dish remained uncovered until the solvent had completely evaporated. The amount of active compound per square centimeter of filter paper varied with the concentration of the solution of active compound used. About 25 test insects were then placed in the Petri dish and it was covered with a glass lid.

The condition of the test insects was continuously observed. The time which was necessary for a 100% knock down effect was determined.

The test insects, the active compounds, the concentrations of the active compounds and the periods of time at which there is a 100% knock down effect can be seen from the following Table 6.

Table 6 (LT test for Diptera Musca domestica) Table 6- Continued (LT test for Diptera Muscu domesticn) Active Concentration of l.'l compound active compound of the solution in by weight 0.002 205 0.2 40' (3) 0.02 105 0.002 240 0.0002 8" 60 K 0.2 40' (4) 0.02 75' 0.002 6" 0.2 40 (I6) 0.02 60' 0.002 135' 00002 x" 0.2 35' (18) 0.02 60' 0002 1 15' 0.0002 6" 0.00002 8" 0.2 30' (5) 0.02 50 0.002 190' 0.0002 8" 0.2 30' (19) 0.02 75' 0.002 205 0.2 20' (27) 0.02 50' 0.002 150' 0.2 50' (36) 0.02 95' Table 6-Continued Table 7-Continued (LT test for Diptera Musca domestica) (LT test for Diptera Aedes acgypti) Active Concentration of LT,0 Active Concentration of compound active compound 5 compound active compound L'I'M,

of the solution of the solution in in by weight by weight 0002 115' 0.002 0.0002 s A 00002 3" a0 '7, 0.2 60 0.2 60 (39) 0.02 75' 10 (18) 0.02 00' 0.002 0" 0.002 120' 0.2 00' 0.2 00' (38) 0.02 135' (5) 0.02 00' 0.002 3'- 0 0.002 180 0.000 1201' 0.2 (10' (19) 0.02 00' 0.002 120' EXAMPLE 11 0.2 00' (271 0.02 00' LT test for Dtptera 0.002 120' Test insects: Aedes aegypti 8-2 13, Solvent: 3CIOI1 3 0:02 20' 2 parts by weight of active compound were dissolved 20 26 8-5 in 1000 parts by volume of solvent. The solution so ob- 0:002 tained was diluted with further solvent to the desired 02 7 7 lower concentrations. (32) 68. 2.5 ml of the solution of active compound were pipet- 12) 0.02 120' ted into a Petri dish. On the bottom of the Petri dish (28) there was a filter paper with a diameter of about 9.5 02 00' cm. The Petri dish remained uncovered until the 501- (6) 8: vent had completely evaporated. The amount of active (20) compound per square centimeter of filter paper var1ed 042 30 (7) 0.02 120' with the concentration of the solut1on of active com- 0002 pound used. About 25 test insects were then placed in 0.2 120' the Petri dish and it is covered with a glass lid. 8'2 The condition of the test insects was continuously ob- (13) 0: 130' served. The time which was necessary for a 100% 02 (30) 0.02 1x0 knock down effect was determined. 02 The test insects, the active compounds, the concen- 38: trations of the active compounds and the periods of (8) Sig time at which there is a 100% knock down effect can 02 00' be seen from the following Table 7. 40 (22) 0.0002 180' Table 7 0,2 00' (9) 0.02 120' (LT test for Diptera Aedes aegypti) 0'002 :,5() Active Concentration of compound active compound LTM (H) 2 l of the solution in (46) 8-3 0 A; by welght 2 60' (1) 0.2 3" 90 (47) 8'9 '28. 38 0 02 120' (2) 0.2 180' (known) 0.2 00' 50 (15) 0.02 120' 0.002 180' 02 EXAMPLE 12 41 002 I 0.2 LD test (42) 0.02 I80: Test insects: Sitophilus granarius (17) 8:3 28, 55 Solvent: acetone 0.002 2 parts by weight of the active compound were dissolved in 1000 parts by volume of the solvent. The solu- (44) 0.02 120 Q2 t1on so obtained was dlluted w1th further solvent to the 8-? 2g: desired lower concentrations. (24) 60 2.5 of the solution of the active compound were pi- 0.2 120: petted into a Petri dish. On the bottom of the Petri dish (45) 8:; '28, there was a filter paper with a diameter of about 9.5 (3) 0.02 120' cm. The Petri dish remained uncovered until the sol- 3-2 65 vent had completely evaporated. The amount of active (4) compound per square centimeter of filter paper varied 8.8g; with the concentration of the solution of active com- I pound used. About 25 test insects were then placed in 10) 0.02 60' the Petri dish and it was covered with a glass lid.

The condition of the test insects was observed 3 days after the commencement of the experiments; the destruction was determined as a percentage.

The active compounds, the concentrations of the active compounds, the test insects and the results can be seen from the following Table 8.

Table 8 (LD test Sitophilus granarius) Concentration of active compound of the solution in by weight Active compound Destruction I00 I00 I00 I00 I00 I00 I00 I00 I00 100 90 I00 I00 I00 90 I00 I00 I00 I00 I00 I00 I00 I00 I00 I00 I00 I00 I00 I00 I00 100 LII C ON ON ON N I00 I00 I00 I00 I00 EXAMPLE l3 On the bottom of the Petri dish there was a filter paper with a diameter of about 9.5 cm. The Petri dish remained uncovered until the solvent had completely evaporated. The amount of active compound per square centimeter of filter paper varied with the concentration of the solution of active compound used. About 25 test insects were then placed in the Petri dish and it was covered with a glass lid.

The condition of the test insects was observed 3 days after commencement of the experiments; the destruction was determined as a percentage.

The active compounds, the concentrations of the active compounds, the test insects and the results can be seen from the following Table 9.

Table 9 (LD test Blatta orientalis) Active Concentration of compound active compound Destruction of the solution in Z in by weight (I) 0.2 0 (known) 0.2 I00 (3) 0.02 I00 0.2 I00 (4) 0.02 60 02 I00 (16) 002 I00 0.2 I00 (18) 0.02 I00 0.002 30 0.2 I00 (5) 0.02 I00 0.2 I00 (I9) 0.02 I00 0.002 30 0.2 I00 (27) 0.02 I00 0.002 30 0.2 I00 (36) 0.02 I00 0.2 I00 (26) 0.02 60 0.2 I00 (32) 0.02 I00 0.002 I00 0.2 I00 (12) 0.02 30 0.2 I00 (20) 0.02 30 0.2 I00 (7) 0.02 60 0.2 I00 (8) 0.02

It will be appreciated that the instant specification and examples are set forth by way of illustration and not limitation, and that various modifications and changes may be made without departing from the spirit and scope of the present invention.

What is claimed is:

1. A 1-carbalkoxy-2-cyano-vinyl-(thiono)-phosphoric(phosphonic) acid ester or ester amide of the formula Rolf in which R and R are alkyl of l to 6 carbon atoms,

R is alkyl, alkoxy or monoalkylamino of I to 6 carbon atoms, or phenyl,

R is hydrogen or alkyl of I to 20 carbon atoms. and

X is oxygen or sulfur.

4. The compound according to claim 1, wherein such compound is ethyl-O-methyl-O-(1-carbisopropoxy-2- cyano-2-methyl)-vinyl-thionophosphonic acid ester of the formula 5. The compound according to claim 1, wherein such compound is 0,0-diethyl-O-( I-carbethoxy-2-cyano-2- methyl)-vinyl-thionophosphoric acid ester of the formula 6. The compound according to claim 1, wherein such compound is methyl-O-isopropyl-O-( l-carbcthoxy-Z- cyanO-Z-methyl)-vinyl-thionoph0sphonic acid ester of the formula S CH 7. The compound according to claim 1, wherein such compound is phenyl-O-ethyl-O-(l-carhethoxy-Z- cyano-2-methyl)-vinyl-thionophosphonic acid ester of the formula 

2. A compound according to claim 1 in which R and R'''' are alkyl of 1 to 4 carbon atoms, R'' is alkyl, alkoxy or monoalkylamino of 1 to 4 carbon atoms or phenyl, and R'''''' is hydrogen or alkyl of 1 to 16 carbon atoms.
 3. The compound according to claim 1, wherein such compound is methyl-O-ethyl-O-(1-carbethoxy-2-cyano-2-methyl)-vinyl-thionophosphonic acid ester of the formula
 4. The compound according to claim 1, whErein such compound is ethyl-O-methyl-O-(1-carbisopropoxy-2-cyano-2-methyl)-vinyl-thionophosphonic acid ester of the formula
 5. The compound according to claim 1, wherein such compound is O,O-diethyl-O-(1-carbethoxy-2-cyano-2-methyl)-vinyl-thionophosphoric acid ester of the formula
 6. The compound according to claim 1, wherein such compound is methyl-O-isopropyl-O-(1-carbethoxy-2-cyano-2-methyl)-vinyl-thionophosphonic acid ester of the formula
 7. The compound according to claim 1, wherein such compound is phenyl-O-ethyl-O-(1-carbethoxy-2-cyano-2-methyl)-vinyl-thionophosphonic acid ester of the formula 